JP2002214740A - Silver halide color photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide color photographic sensitive material which exhibits excellent blocking property, electrification characteristics, scratching resistance, smoothness and adhesion property with a tape, which is improved in the aggregation property of the coating liquid used for the manufacture, which decreases coating failure, and which generates feeding torque for supplying the photosensitive material. SOLUTION: In the silver halide color photographic sensitive material having red photosensitive layers, green photosensitive layers, blue photosensitive layers and non-photosensitive layers on one surface of a supporting body, the non- photosensitive layer farthest from the supporting body contains a compound expressed by the formula of H.Rf-(CH2)n-L-Xm and a monodispersion matting agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material, and more particularly to a silver halide color photographic light-sensitive material having improved physical properties of a film by adding a specific fluorine-based surfactant.

[0002]

2. Description of the Related Art A silver halide color photographic light-sensitive material (hereinafter, also simply referred to as a light-sensitive material) is basically formed by coating a support with a hydrophilic colloid composition containing a light-sensitive silver halide and a color coupler. And dried.

[0003] In such a hydrophilic colloid composition, a photographically useful substance is prepared by adding it to the hydrophilic colloid composition as a dissolved substance or a dispersion, and its solubility, dispersibility, liquid physical properties, and solution stability. Generally, a surfactant is appropriately selected and used for the purpose of improving the property.

On the other hand, a silver halide color photographic light-sensitive material is provided with light-sensitive layers having red, green and blue sensitivities, respectively, and these layers have different sensitivities in order to secure different sensitivities. A plurality of different layers are provided, and further, an intermediate layer is provided between each photosensitive layer as necessary, and further, each function such as an antihalation layer, a yellow filter layer, an ultraviolet absorbing layer, and a protective layer is provided. Since a non-photosensitive functional layer is provided, the total number of photographic constituent layers of a recent photographic material generally exceeds 10 layers.

In order to coat a large number of layers in a well-balanced manner on a support having an undercoat layer as described above, the coating liquid of each constituent layer is appropriately set to a surface tension value having a desired balance. It is important to adjust the surface tension
Generally, various surfactants are selected and used.

Further, it is known that the physical durability of a silver halide color photographic light-sensitive material in a dry state or a high humidity state, static electricity resistance, suitability for a camera, etc., largely depend on the characteristics of the surfactant used. ing.

Therefore, the role of a surfactant in a silver halide color photographic material is extremely important.
Many researches and developments have been made to achieve the above-mentioned problem, but in recent years, more severe requirements have been made on the characteristics, but it is insufficient to satisfy the characteristics.

In view of the above problems, in recent years, many of the above-mentioned problems have been improved by the development of fluorine-based surfactants, but on the other hand, there are specific problems caused by the strong surface orientation of the fluorine-based surfactants. It has the disadvantage of poor adhesion to various tapes used in the manufacturing process of silver halide color photographic light-sensitive materials or in the development process, and has an excellent physical property when using fluorine-based surfactants. A major challenge was to maintain the effect of improving the properties and achieve an improvement in tape adhesion.

[0009]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems, and has as its object to provide excellent blocking properties, charging characteristics, scratch resistance and slipperiness, a small feeding torque of a photosensitive material, and An object of the present invention is to provide a silver halide color photographic light-sensitive material having excellent tape adhesion. In addition, another object of the present invention is to improve the cohesiveness of a coating solution used for producing a light-sensitive material and to reduce coating failure.

[0010]

The above object of the present invention has been attained by the following constitutions.

1. On one side of the support, a red-sensitive layer,
In a silver halide color photographic light-sensitive material having a green light-sensitive layer, a blue light-sensitive layer, and a non-light-sensitive layer, the non-light-sensitive layer farthest from the support is a monodisperse compound containing the compound represented by the formula (1). A silver halide color photographic light-sensitive material characterized by containing a hydrophilic matting agent.

2. On one side of the support, a red-sensitive layer,
In a silver halide color photographic light-sensitive material having a green light-sensitive layer, a blue light-sensitive layer, and a non-light-sensitive layer, the non-light-sensitive layer farthest from the support contains the compound represented by the formula (1) and an alkali-soluble compound. A silver halide color photographic light-sensitive material comprising a matting agent.

3. On one side of the support, a red-sensitive layer,
In a silver halide color photographic light-sensitive material having a green light-sensitive layer, a blue light-sensitive layer, and a non-light-sensitive layer, the non-light-sensitive layer furthest from the support comprises a compound represented by the formula (1) and an aqueous polyurethane. A silver halide color photographic light-sensitive material comprising:

4. On one side of the support, a red-sensitive layer,
In a silver halide color photographic light-sensitive material having a green light-sensitive layer, a blue light-sensitive layer, and a non-light-sensitive layer, the non-light-sensitive layer furthest from the support comprises a compound represented by the above formula (1) and a polyorgano compound. A silver halide color photographic light-sensitive material characterized by containing siloxane.

[0015] 5. On one side of the support, a red-sensitive layer,
In a silver halide color photographic light-sensitive material having a green light-sensitive layer, a blue light-sensitive layer and a light-insensitive layer, the light-insensitive layer farthest from the support is ion-exchanged with the compound represented by the formula (1). A silver halide color photographic light-sensitive material comprising processed gelatin.

6. On one side of the support, a red-sensitive layer,
In a silver halide color photographic light-sensitive material having a green light-sensitive layer, a blue light-sensitive layer, and a non-light-sensitive layer, the non-light-sensitive layer farthest from the support is the same as the compound represented by the formula (1). Gelatin having a dot of 5.0 or more
A silver halide color photographic light-sensitive material, characterized in that it contains at least 10% by mass.

[7] On one side of the support, a red-sensitive layer,
In a silver halide color photographic light-sensitive material having a green light-sensitive layer, a blue light-sensitive layer and a non-light-sensitive layer, the non-light-sensitive layer furthest from the support contains the compound represented by the general formula (1), When the surface pH of the silver halide color photographic light-sensitive material is in the range of 5.6 to 6.2 and the silver potential of the coating film is 8
A silver halide color photographic light-sensitive material, which is in the range of 0 to 150 mV.

[8] On one side of the support, a red-sensitive layer,
In a silver halide color photographic light-sensitive material having a green light-sensitive layer, a blue light-sensitive layer and a non-light-sensitive layer, the non-light-sensitive layer furthest from the support contains the compound represented by the general formula (1), A silver halide color photographic light-sensitive material characterized in that at least one of the constituent layers is hardened with at least one compound selected from the general formulas (2) and (3).

9. On one side of the support, a red-sensitive layer,
In a silver halide color photographic light-sensitive material having a green light-sensitive layer, a blue light-sensitive layer and a non-light-sensitive layer, the non-light-sensitive layer furthest from the support contains the compound represented by the general formula (1), A silver halide color photographic light-sensitive material characterized in that the number of constituent layers is 10 or more and the layers are formed by simultaneous multi-layer coating.

[10] On one side of the support, in a silver halide color photographic light-sensitive material having a red-sensitive layer, a green-sensitive layer, a blue-sensitive layer and a non-light-sensitive layer, the non-light-sensitive layer farthest from the support is A silver halide color photographic light-sensitive material comprising a mixture of an anionic surfactant and a cationic surfactant, at least one of which is a compound represented by formula (1).

Hereinafter, the present invention will be described in detail. (Fluorine-based surfactant) The compound represented by the general formula (1) according to the present invention substantially means a fluorine-containing atom surfactant (hereinafter also referred to as a fluorine-based surfactant).

In the general formula (1), Rf represents an alkylene group containing at least one fluorine atom;
L is a single bond or - represents a (CH _{2) n} group and linking group attached at a heteroatom or a carbonyl group, X represents a hydroxy group, an anionic group, a cationic group or amphoteric group. n represents an integer of 2 or more and 5 or less, and m represents an integer of 1 or more.

In the general formula (1), Rf represents an alkylene group containing at least one fluorine atom, preferably having 3 to 15 carbon atoms, more preferably 4 to 1 carbon atoms.
It is preferably 0, and particularly preferably 4 to 7. n represents an integer of 2 or more and 5 or less, and preferably 2 or more and 4 or less. m represents an integer of 1 or more;
It is preferably at least 3 and at most 3. L is or a single bond - (CH ₂₎ represents an _n group and hetero atom or a linking group bonded through a carbonyl group, a nitrogen as the hetero atom, oxygen, sulfur atom.

X represents a hydroxy group, an anionic group, a cationic group or an amphoteric group.
Carboxyl group, sulfonic acid group, phosphoric acid group is preferred,
As the counter cation, an alkali metal ion such as a sodium ion and a potassium ion, an ammonium ion and the like are preferable. The cationic group is preferably a quaternary alkylammonium group, and the counter anion is preferably a halide ion, p-toluenesulfonic acid ion or the like. As the amphoteric group, those in which the above-mentioned cationic group and anionic group are bonded are preferable.

Hereinafter, specific examples of preferred fluorine-based surfactants that can be used in the present invention are shown, but the fluorine-based surfactants that can be used in the present invention are not limited to these.

[0026] Anionic Surfactant _{1: HC 5 F 10 - (} CH 2) 2 -O-PO (ONa) 2 2: HC 6 F 12 - (CH 2) 2 -O-PO (ONa) 2 _{3: HC 8 F 16 - (} CH 2) 2 -O-PO (ONa) 2 4: HC 10 F 20 - (CH 2) 2 -O-PO (ONa) 2 5: HC 12 F 24 - (CH 2 _{) 2 -O-PO (ONa)} 2 6: HC 4 F 8 - (CH 2) 3 -O-PO (ONa) 2 7: HC 5 F 10 - (CH 2) 3 -O-PO (ONa) 2 _{8: HC 6 F 12 - (} CH 2) 3 -O-PO (ONa) 2 9: HC 7 F 14 - (CH 2) 3 -O-PO (ONa) 2 10: HC 5 F 10 - (CH 2 _{) 2 -COONa 11: HC 6 F} 12 - (CH 2) 2 -COONa 12: HC 8 F 16 - (CH 2) 2 -COONa 13: HC 10 F 20 - (CH 2) 2 -COONa 14: HC ₁₂ F ₂₄ — (CH ₂ ) ₂ —COONa 15: HC ₆ F ₁₂ — (CH ₂ ) ₂ —S—C ₂ H ₄ —COON
_{H 4 16: HC 7 F 14} - (CH 2) 2 -S-C 2 H 4 -COON
_{H 4 17: HC 6 F 12} - (CH 2) 3 -COONa 18: HC 7 F 14 - (CH 2) 3 -COONa 19: HC 6 F 12 - (CH 2) 2 -O-CH (COON
_{a) 2 20: HC 6 F} 12 - (CH 2) 2 -NHCOCH (COO
_{Na) 2 21: HC 6 F} 12 - (CH 2) 2 -NHCOCH 2 COON
_{a 22: HC 6 F 12 -} (CH 2) 2 -O-C 2 H 4 COONa 23: HC 5 F 10 - (CH 2) 2 -O-SO 3 Na 24: HC 6 F 12 - (CH 2) _{2 -OC 3 H 6 -SO 3 Na} 25: HC 8 F 16 - (CH 2) 2 -NHCOCH 2 -SO 3
_{Na 26: HC 10 F 20 -} (CH 2) 2 -O-SO 3 Na 27: HC 12 F 24 - (CH 2) 2 -SO 3 Na 28: HC 4 F 8 - (CH 2) 3 -OC 3 _{H 6 -SO 3 Na 29: HC} 5 F 10 - (CH 2) 3 -NHCOCH 2 -SO 3
Na 30: HC ₆ F ₁₂ — (CH ₂ ) ₃ —O—SO ₃ Na 31: HC ₇ F ₁₄ — (CH ₂ ) ₂ —NHCOC ₂ H ₄ SO ₃ N
_{a 32: HC 6 F 12 -} (CH 2) 2 -O-SO 3 Na 33: HC 6 F 12 - (CH 2) 2 -NHCOCH 2 -SO 3
Na 34: HC ₆ F ₁₂ — (CH ₂ ) ₂ —OCH ₂ —SO ₃ Na 35: HC ₆ F ₁₂ — (CH ₂ ) ₂ —OC ₂ H ₄ O—SO ₃ Na [Cationic surfactant] 36 _{: HC 5 F 10 - (CH} 2) 2 -CONH (CH 2) 3 N +
^{_{(CH 3) 3, Br -}} 37: HC 6 F 12 - (CH 2) 2 -CONH (CH 2) 3 N +
^{_{(CH 3) 3, Br -}} 38: HC 8 F 16 - (CH 2) 2 -NHCO (CH 2) 3 N +
^{_{(CH 3) 3, Br -}} 39: HC 10 F 20 - (CH 2) 2 -NHCO (CH 2) 3 N
^{_{+ (CH 3) 3, Br}} - 40: HC 12 F 24 - (CH 2) 2 -NHCO (CH 2) 3 N
^{_{+ (CH 3) 3, Br}} - 41: HC 4 F 8 - (CH 2) 3 -NHCO (CH 2) 3 N +
^{_{(CH 3) 3, Br -}} 42: HC 5 F 10 - (CH 2) 3 -NHCO (CH 2) 3 N +
^{_{(CH 3) 3, Br -}} 43: HC 6 F 12 - (CH 2) 3 -NHCO (CH 2) 3 N +
^{_{(CH 3) 3, Br -}} 44: HC 7 F 14 - (CH 2) 2 -NHCO (CH 2) 2 N +
^{_{(CH 3) 3, Br -}} 45: HC 6 F 12 - (CH 2) 2 -OCH 2 N + (CH 3) 2
^{_{(C 2 H 4 OH),}} Br - 46: HC 6 F 12 - (CH 2) 2 -OCH 2 N + (CH 3) 2
^{_{(C 2 H 5), Br}} - 47: HC 6 F 12 - (CH 2) 2 -OC 3 H 6 N + (C
^{_{H 3) 3, Br - 48}} : HC 6 F 12 - (CH 2) 2 -OCH 2 NHCOC 2 H 4
^{_{N + (CH 3) 3,}} Br - [Nonionic Surfactant] _{49: HC 5 F 10 - (} CH 2) 2 -OC 3 H 6 -OH 50: HC 6 F 12 - (CH 2) 2 -OC _{3 H 6 -OH 51: HC 8} F 16 - (CH 2) 2 -OC 3 H 6 -OH 52: HC 10 F 20 - (CH 2) 2 -OC 3 H 6 -OH 53: HC 12 F 24 - _{(CH 2) 2 -OC 3 H} 6 -OH 54: HC 4 F 8 - (CH 2) 3 -OC 3 H 6 -OH 55: HC 5 F 10 - (CH 2) 3 -OC 3 H 6 -OH _{56: HC 6 F 12 - (} CH 2) 3 -OC 3 H 6 -OH 57: HC 7 F 14 - (CH 2) 3 -OC 3 H 6 -OH 58: HC 6 F 12 - (CH 2) 2 _{-OC 2 H 4 -OH 59: HC} 6 F 12 - (CH 2) 2 -NHCOC 2 H 4 OH 60: HC 6 F 12 - (CH 2) 2 - (OC 2 H 4) 2 -OH 61: HC ₆ F _{1 2 - (CH 2) 2 -O} -C (C 2 H 4 OH) 3 [Amphoteric surfactants] _{62: HC 5 F 10 (CH} 2) 2 -NHCOC 2 H 4 N + (CH
^{_{3) 2 CH 2 COO - 63}} : HC 6 F 12 (CH 2) 2 -NHCOC 2 H 4 N + (CH
^{_{3) 2 CH 2 COO - 64}} : HC 8 F 16 (CH 2) 2 -NHCOC 2 H 4 N + (CH
^{_{3) 2 CH 2 SO 3 -}} 65: HC 10 F 20 (CH 2) 2 -NHCOC 2 H 4 N + (C
^{_{H 3) 2 CH 2 COO -}} 66: HC 12 F 24 (CH 2) 2 -NHCOC 2 H 4 N + (C
_{H 3) 2 CH 2 SO 3} - 67: HC 4 F 8 (CH 2) 3 -NHCOC 2 H 4 N + (C
^{_{H 3) 2 CH 2 COO -}} 68: HC 5 F 10 (CH 2) 3 -NHCOC 2 H 4 N + (CH
^{_{3) 2 CH 2 COO - 69}} : HC 6 F 12 - (CH 2) 3 -OCH 2 N + (CH 3) 2
^{_{C 2 H 4 SO 3 - 70}} : HC 7 F 14 - (CH 2) 3 -OCH 2 N + (CH 3) 2
^{_{C 2 H 4 SO 3 - 71}} : HC 6 F 12 - (CH 2) 2 -OCH 2 CH (CO
_{^{O -) N + (CH 3}} ) 3 72: HC 6 F 12 - (CH 2) 2 -OCH 2 N + (CH 3) 2
C ₂ H ₄ COO ^- The synthesis method of the fluorine-based surfactant may be Kohyo No. 10-500950, the Nos. 11-504360 reference.

In the invention according to claim 10, when the anionic surfactant represented by the general formula (1) and the cationic surfactant represented by the general formula (1) are used in combination, It has a partial chemical structure [H-Rf-
It is preferable that the (CH ₂ ) _n −] portion is approximate, and particularly preferably the same. The approximation in the present invention means that the difference in the number of carbon atoms in the partial chemical structure between the anionic surfactant and the cationic surfactant is within 2 or the difference in the number of fluorine atoms in the partial chemical structure is 4 or less. Means at least one of the following cases.
Furthermore, it is preferable that the partial chemical structures including L which is a mere bond or a linking group are similar, and it is particularly preferable that they are the same.

In the light-sensitive material of the present invention, the content of the fluorine-based surfactant is 0.01 to 0.01 with respect to the hydrophilic layer colloid.
It is preferably in the range of 3% by mass, particularly preferably in the range of 0.02 to 1% by mass. When the content of the fluorine-based surfactant is less than the above range, the effect of the present invention is small, and when the content is more than the above range, the coating solution is easily foamed or easily aggregated. In addition, it is not preferable because it deteriorates the surface of the formed coating film.

(Monodisperse matting agent) The invention according to claim 1 is characterized in that the non-photosensitive layer farthest from the support contains a monodisperse matting agent together with the above-mentioned fluorine-containing surfactant. .

Hereinafter, the monodisperse matting agent according to the present invention will be described. The matting agent in the present invention refers to water-insoluble or hardly water-soluble inorganic or organic particles. Examples of the inorganic particles include silica, colloidal silica, titanium oxide, glass powder, and barium sulfate. Examples of the organic particles include synthetic polymers such as polystyrene, polymethyl methacrylate, polycarbonate, and polyacrylate copolymers, and natural products such as starch and corn starch. In particular, the acrylic ester / acrylic acid copolymer can be completely or partially removed in the development step by adjusting the molar ratio,
This is useful because it can be left behind. In the present invention, a matting agent having the property of remaining at least partially after the development processing is preferable.

The monodisperse matting agent referred to in claim 1 is a matting agent having a narrow particle size distribution. In order to obtain the effects of the present invention, the monodispersity of the monodisperse matting agent is 0.33. It is preferably at most 0.30, more preferably at most 0.30, particularly preferably at most 0.28. Although the ideal lower limit is 0, a material in which the particle diameters of all the matting agent particles completely match has not been obtained industrially.

The monodispersity referred to in the present invention is a value represented by (standard deviation of particle size distribution / average particle size) calculated on the basis of a sphere equivalent diameter measured by a Coulter counter.

In the invention according to the first aspect, a polymer forming a particularly preferred matting agent is a compound represented by the following general formula [P].

[0034]

Embedded image

Wherein R ₁ , R ₂ and R ₃ each represent a hydrogen atom, an alkyl group or an aryl group; R ₄ and R ₅ each represent an alkyl group, an aryl group or a heterocyclic group;
M represents a hydrogen atom or a cation, x, y and z each represent a molar ratio of the ethylenically unsaturated compound as a raw material, and z / (x + y) <0.30.

The alkyl group represented by R ₁ , R ₂ and R ₃ includes, for example, methyl and ethyl, and the aryl group includes, for example, phenyl.

The alkyl group represented by R ₄ and R ₅ includes, for example, methyl, ethyl, 2-methoxyethyl,
-Hydroxyethyl, i-propyl, butyl, t-butyl, 2-ethylhexyl and the like. These alkyl groups may be substituted, and as the aryl group, for example, phenyl, p-tolyl, p-methoxyphenyl , Naphthyl and the like, and these aryl groups may be substituted. Examples of the heterocyclic group include imidazolyl, pyrazolyl, triazolyl, tetrazolyl, pyridyl, thiazolyl, and oxazolyl. These heterocyclic groups may be substituted.

As the cation represented by M, for example,
Sodium, potassium, ammonium and the like can be mentioned.

X, y and z representing the molar ratio of the ethylenically unsaturated compound as each raw material are 0 <x ≦ 100, 0
≦ y <100, 0 ≦ z <100, and z / (x + y)
<0.30, preferably z / (x + y) <0.
20. When the value of z / (x + y) is 0.30 or more, the residual after the developing process is too small, and the physical characteristics after the developing process may be deteriorated.

In the invention according to claim 1, the average particle size of the monodisperse matting agent is preferably 0.5 to 20 μm, more preferably 1 to 10 μm, and particularly preferably 1.5 to 5 μm.
m.

Table 1 shows specific examples of the polymer represented by the general formula [P] which forms the preferred matting agent particles according to the present invention, and the composition of the monomer is represented by a molar ratio.

[0042]

[Table 1]

In Table 1, MMA is methyl methacrylate, EMA is ethyl methacrylate, BMA is butyl methacrylate, MAA is methacrylic acid, AA
Represents acrylic acid.

The polymers represented by the general formula [P] are described in US Pat. Nos. 4,301,240 and 3,767,448.
No. 2,992,101, JP-A-60-1266.
No. 44 and the like.

The polymerization degree of the polymer represented by the general formula [P] forming the matting agent is from 3,000 to 100 as an average molecular weight.
It is preferably 10,000, and more preferably 5,000 to 50,000.

In the invention according to the first aspect, any known method may be used to adjust the degree of monodispersion of the monodisperse matting agent particles. For example, Japanese Unexamined Patent Application Publication No.
The dispersion method of the photographic additive described in the above item can be utilized. In addition, it may be carried out by a so-called classification method disclosed in JP-A-5-289225, but it is not preferred because complicated operations are required in production, many waste parts are required, and the yield is low. Preferable methods for preparing a monodisperse polymer matting agent include a dispersion polymerization method in which the monomer concentration is lowered, a nozzle ejection method in which the monomer is discharged, a swelling seed polymerization method in which the monomer is swollen and polymerized, and a seed method. There are a two-stage swelling polymerization method in which a swelling aid is applied, a dynamic swelling polymerization method in which a monomer is precipitated in a seed, and the like, but as a method for producing a monodisperse matting agent according to the present invention, a nozzle ejection method is effective. . That is, a method in which a solution of a polymer dissolved in a low-boiling organic solvent (for example, ethyl acetate, butanol, or the like) is jetted into stirring water at a constant speed from a fine nozzle having a controlled diameter. Further, a polymer matting agent having a desired dispersibility is prepared by appropriately adjusting the solution temperature, stirring conditions, addition of a protective colloid agent, a surfactant, and salts, and the temperature, concentration, and jetting speed of the polymer solution. Can be. By this method,
Not only the adjustment of the average particle size but also the adjustment of the degree of monodispersion can be effectively performed. Commercially available products include acrylic powders (MX-150, 3
00, 500, 1000, 1500) can also be used.

The addition amount of the monodisperse matting agent is 1 to 300 mg, preferably 3 to 200 mg per m ² .
If the amount is less than 1 mg, the effect of using the monodisperse matting agent is not exhibited, and if it is more than 300 mg, the physical properties of the coating film are deteriorated, which is not preferable.

(Alkali-Soluble Matting Agent) The invention according to claim 2 is characterized in that the non-photosensitive layer farthest from the support contains an alkali-soluble matting agent together with the above-mentioned fluorine-based surfactant.

The following is a description of the second aspect of the present invention.
The alkali-soluble matting agent will be described.

The alkali-soluble matting agent is not particularly limited as long as it contains a carboxyl group and the like and is soluble in an aqueous alkali solution such as a developing solution. It does not have to have the property.

As the alkali-soluble matting agent, a vinyl polymer or a polyurethane compound is preferably used. Here, the term "soluble in alkaline water" means that an aqueous alkali solution (0.1 mol / L sodium hydroxide solution as a guide) is added to an aqueous dispersion containing 3% by mass of a latex of a matting agent, and the pH becomes 10 When the solution becomes transparent, it is defined that the alkali-soluble matting agent has been solubilized.

As the vinyl polymer, JP-A-8-9
No. 5190, paragraphs [0033] to [0048]
Can be used.

As a method for preparing the alkali-soluble matting agent according to the present invention, generally known radical polymerization methods (for example, Takayuki Otsu and Masayoshi Kinoshita, “Experimental Method for Polymer Synthesis”, Kagaku Dojin, 1972 , Pages 124 to 154), emulsion polymerization,
Solution polymerization is preferred, and emulsion polymerization is particularly preferred.

It is particularly preferable that the alkali-soluble matting agent according to the second aspect has the monodispersity according to the first aspect.

(Aqueous Polyurethane) The invention according to claim 3 is characterized in that the non-photosensitive layer farthest from the support contains the fluorine-based surfactant and the aqueous polyurethane. Characteristics (slipperiness, scratch resistance, etc.) can be obtained.

The aqueous polyurethane in the present invention refers to a polyurethane having a hydrophilic group in a molecule and capable of forming a stable dispersion in water, and can be obtained as an aqueous polyurethane dispersion. The preparation of aqueous polyurethane dispersions is well known in the art, and anionic, cationic or nonionic stabilized aqueous polyurethane dispersions can be prepared.

The anionically stabilized polyurethane dispersions are usually provided with comonomers functionalized with carboxylate or sulfonate, for example, suitably hindered dihydroxycarboxylic acid (dimethylolpropionic acid), or dihydroxysulfonic acid. It can be obtained by using a functionalized comonomer. Also, the cationically stabilized polyurethane dispersion can be prepared by using a polyurethane into which a diol containing a tertiary nitrogen atom has been introduced. Tertiary nitrogen atoms are converted to quaternary ammonium ions by adding a suitable alkylating agent or acid. Also, nonionic stabilized polyurethane dispersions can be prepared using a diol or diisocyanate comonomer having a branched polyethylene oxide chain.

Polyurethane dispersions have colloidally stable properties over a wide pH range, and nonionic and anionic stabilizing combinations are effective for obtaining micronization and high stability. .

In the invention according to the third aspect, polyols useful for preparing the aqueous polyurethane dispersion include diols (for example, ethylene glycol, butylene glycol, neopentyl glycol, hexanediol or a mixture of any of these) and dicarboxylic acid. Polyester polyols produced from acids or their anhydrides (eg, succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, maleic acid and anhydrides of these acids); such as caprolactone Polylactone obtained by reacting lactone and diol; polyether such as polypropylene glycol; acrylic ester such as alkyl acrylate or alkyl methacrylate and carboxyl, hydroxyl, cyano group and / or Include a hydroxyl-terminated polyacrylic derivatives produced by addition polymerization of ethylenically unsaturated monomers containing functional groups such as Rishijiru group.

Examples of usable diisocyanates include toluene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, ethylethylene diisocyanate, 2,3-dimethylethylene diisocyanate,
-Methyltrimethylene diisocyanate, 1,3-cyclopentylene diisocyanate, 1,4-cyclohexylene diisocyanate, 1,3-phenylene diisocyanate, 4,4′-biphenylene diisocyanate,
Examples thereof include 1,5-naphthalenediisocyanate, bis- (4-isocyanatocyclohexyl) -methane, 4,4'-diisocyanatodiphenyl ether, and tetramethylxylene diisocyanate.

For the preparation of an anionically stabilized polyurethane, a compound having a group capable of forming an anion which is reactive with an isocyanate group to introduce an anion group is used. Examples of the compound having a group capable of forming an anion include dihydroxypropionic acid, dimethylolpropionic acid, dihydroxysuccinic acid, and dihydroxybenzoic acid. Other suitable compounds include monosaccharides, such as polyhydroxy acids produced by oxidizing gluconic acid, sugar acids, mucinic acids, and the like. These acids are converted into anionic groups for neutralization to make them water-dispersible. For example, a tertiary amine can be used to generate an anionic group. These tertiary amines include, for example, trimethylamine, triethylamine, dimethylaniline, diethylaniline, triphenylamine and the like.

Diamines are used for extending the chain of the polyurethane. Suitable diamines include, for example, ethylenediamine, diaminopropane, hexamethylenediamine, hydrazine, aminoethylethanolamine and the like.

Examples of the water-based polyurethane that can be used in the present invention include water-dispersible siloxane-containing polyurethanes described in US Pat. Nos. 5,876,910 and 5,932,405; 8
Aqueous dispersible polyurethane described in JP-A-04,360 /
A dispersion liquid of a vinyl polymer is mentioned, and these can be preferably used. Further, a preferable polyurethane compound having a carboxyl group is disclosed in JP-A-8-9 / 1996.
No. 5190, paragraphs [0048] to [0056]. Further, preferred aqueous polyurethanes that can be used in the present invention are commercially available. Examples of these commercially available aqueous dispersible polyurethanes include Witcobond available from Witco.
W232 and W242; F. Goodrich
Sancure 898, 815D, 2 available from the company
260 and 12684, and Zeneca Resi
Neorez R966 available from ns.

(Polyorganosiloxane) The invention according to claim 4 is characterized in that the non-photosensitive layer farthest from the support contains a fluorine-based surfactant and a polyorganosiloxane. Is preferred because the excellent effects of the present invention are exhibited. The polyorganosiloxane also functions as a slip agent.

In the present invention, known polyorganosiloxanes such as polydimethylsiloxane, polydiethylsiloxane, polystyrylmethylsiloxane and polymethylphenylsiloxane can be used. In particular, polydimethylsiloxane and polyorganosiloxane containing an ester having a long-chain alkyl group are preferable. The carbon number of the long-chain alkyl group is preferably 10 or more, more preferably 12 or more. Further, the upper limit of the number of carbon atoms in the long-chain alkyl group is preferably 60 or less, more preferably 50 or less. The dispersion stability of the polyorganosiloxane is further enhanced by the fluorine-based surfactant of the present invention.

Representative examples of the polyorganosiloxane used in the invention according to claim 4 are shown below together with their trade names, but the polyorganosiloxane that can be used in the invention is not limited thereto. Absent.

A-1: Dimethylpolysiloxane (KF-92 manufactured by Shin-Etsu Chemical Co., Ltd.) A-2: Dimethyl polysiloxane (KF manufactured by Shin-Etsu Chemical Co., Ltd.)
-96-20cs) A-3: Dimethylpolysiloxane (KF, manufactured by Shin-Etsu Chemical Co., Ltd.)
A-4: Dimethyl polysiloxane (KF, manufactured by Shin-Etsu Chemical Co., Ltd.)
-96-500cs) A-5: Dimethylpolysiloxane (KF, manufactured by Shin-Etsu Chemical Co., Ltd.)
-96-1000cs) A-6: Dimethylpolysiloxane (KF, manufactured by Shin-Etsu Chemical Co., Ltd.)
-96H-6000cs) A-7: Dimethylpolysiloxane (KF, manufactured by Shin-Etsu Chemical Co., Ltd.)
-96H-12500cs) A-8: Polydimethylsiloxane-alkylene oxide copolymer (PS074, manufactured by Chisso) A-9: Polyester-modified dimethylpolysiloxane (BYK-310, manufactured by BYK Japan) A-10: Polyester containing hydroxyl group Modified dimethylpolysiloxane (BYK-37 manufactured by BYK Japan KK)
0) (Ion exchange treated gelatin) In the invention according to claim 5,
The non-photosensitive layer furthest from the support is characterized by containing a fluorine-based surfactant and an ion-exchanged gelatin, and the use of this constitution is preferable because the excellent effects of the present invention are exhibited. That is, they have found that the fluorine-based surfactant according to the present invention functions extremely effectively in gelatin subjected to ion exchange treatment.

Hereinafter, the ion exchange treated gelatin used in the present invention will be described. As the binder for forming the hydrophilic colloid layer containing the fluorine-containing surfactant according to the present invention, generally, gelatin is preferably used, for example, lime-treated gelatin or enzyme-treated gelatin, or a hydrolyzate or enzymatic degradation product of gelatin. Further, modified gelatin such as phthalated gelatin can also be used.

Further, hydrophilic colloids other than gelatin can be preferably used by mixing with gelatin. For example, proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates; sugar derivatives such as sodium alginate, dextran and starch derivatives;
Polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylimidazole, etc. Can be used together.

In the invention according to claim 5, when the fluorine-based surfactant is applied to a non-photosensitive layer farthest from a support, that is, a so-called protective layer, ion-exchange-treated gelatin is applied.

The ion-exchanged gelatin used in the present invention is obtained by subjecting gelatin to ion-exchange treatment.
Polyvalent metal ions such as Zn are excluded. The ion-exchanged gelatin used in the invention according to claim 5 is preferably one in which the content of polyvalent metal ions such as Ca, Mg, Al, and Zn is reduced to 500 ppm or less by ion exchange treatment.
More preferably, it is 100 ppm or less.
m or less is particularly preferable.

The ion-exchange treatment of gelatin is obtained by extracting gelatin from raw materials such as beef bone and pig skin and then performing ion exchange using an ion-exchange resin (for example, IRA type from Rohm and Haas). Can be.

The quantification of the polyvalent metal ion content in the gelatin after the ion exchange treatment should be carried out according to the method described in the sixth edition of the photographic gelatin test method (abbreviation: Bagii method) established by the Joint Committee for Gelatin Test Methods. Can be.

(Gelatin having an isoelectric point of 5.0 or more) In the invention according to claim 6, the non-photosensitive layer furthest from the support contains the fluorine-based surfactant, and The binder is characterized by containing 10% by mass or more of gelatin having an isoelectric point of 5.0 or more. Use of this configuration is preferable because excellent effects are exhibited. That is, gelatin having an isoelectric point of 5.0 or more is
It has been found that the fluorine-based surfactant functions extremely effectively when contained in an amount of not less than mass%.

Hereinafter, the gelatin having an isoelectric point of 5.0 or more according to the present invention will be described. Gelatin having an isoelectric point of 5.0 or more may be contained in the binder in an amount of 10% by mass or more, and preferably 15 to 100% by mass. If the content of the gelatin having an isoelectric point of 5.0 or more in the binder falls within the above range, gelatin having an isoelectric point of less than 5.0 may be used in combination, but it is not convenient to prepare a silver halide emulsion. In addition, it is preferable that all of the gelatin used be gelatin having an isoelectric point of 5.0 or more.

The isoelectric point of the gelatin used in the present invention may be at least 5.0, but it is preferable to use gelatin having an isoelectric point of 5.0 to 10.0.

The isoelectric point of gelatin used in the present invention is defined as p when the salt ion is completely removed from the gelatin solution.
H, ie, iso-ion point. In general, acid-treated gelatin corresponds to gelatin having an isoelectric point of 5.0 or more. These gelatins are generally commercially available, and commercially available products include, for example, # 99 (manufactured by STOESS), # 9
50 (manufactured by Nitta Gelatin), #PS, and #ABA (manufactured by Nippi).

(Film Surface pH, Coating Silver Potential) In the invention according to claim 7, the non-photosensitive layer farthest from the support contains the fluorine-containing surfactant, and the film surface of the photosensitive material surface p
H is in the range of 5.6 to 6.2, and the silver potential of the coating film is in the range of 80 to 150 mV. By adopting this configuration, excellent effects of the present invention are exhibited. It is found that it is done.

The film surface pH of the light-sensitive material of the present invention and the silver potential of the coating film will be described below. The film surface pH of the light-sensitive material in the present invention means the pH of the film surface of the outermost layer on the side of the photographic light-sensitive material on which the silver halide emulsion layer is formed.

The pH of the membrane surface can be measured by using a microsyringe to drop 20 microliters of pure water per cm ² of the measurement sample onto the membrane surface, applying a plate electrode, and reading the pH value 30 seconds later. As a plate electrode, for example, a composite electrode GST-S21 manufactured by Toa Denpa Kogyo KK
3F can be used.

In the present invention, the pH of the film surface of the light-sensitive material can be adjusted by a generally used method. For example, the pH of the coating solution for the outermost surface layer is adjusted to an acid or alkali. Can be adjusted. These acids or alkalis may be mixed in the coating solution in advance, or may be added just before coating to adjust the pH. Examples of the pH adjusting agent of the coating solution include acids such as hydrochloric acid, sulfuric acid, formic acid, acetic acid, citric acid, and boric acid, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, potassium citrate, lithium citrate, Alkali such as sodium acetate, potassium acetate, and ammonia can be used.

In the invention according to claim 7, the pH of the membrane surface is set to 5.
The value is 6 to 6.2, but it is more effective that the value is 5.8 to 6.0. When the film surface pH exceeds 6.5, the raw preservability of the light-sensitive material is remarkably reduced. Conversely, when the film surface pH is less than 5.0, a crosslinking reaction by a hardening agent required for the light-sensitive material is remarkable. It is not preferable because it becomes slow.

The silver potential of the coating film is the silver potential of the entire coating film. For example, 500 cm ² of a light-sensitive material is cut into strips, immersed in 100 ml of pure water for 6 hours in a dark room, and then charged with a commercially available saturated silver powder. It can be determined by measuring using a silver ion electrode using a silver chloride electrode as a reference electrode. At this time, when a non-photosensitive layer such as a backing layer is provided on the side opposite to the silver halide emulsion side, the non-photosensitive layer is removed beforehand.

In the present invention, the silver potential of the coating film is from 80 to 1
It is 50 mV, preferably 90 to 140 mV, particularly preferably 100 to 130 mV.

The silver potential of the coating film is adjusted by adding a compound having a function of adjusting the silver potential, for example, AgNO ₃ , KBr, NaBr, KCl to a coating solution for forming each constituent layer of the photosensitive material.
The desired coating silver potential can be obtained by appropriately adding an aqueous solution such as

The coating solution to which the aqueous solution for adjusting the silver potential is added may be a coating solution for forming a non-photosensitive layer farthest from the support for adjusting the silver potential of the coating film, and may be used for forming an adjacent layer or other layers. It may be a constituent coating liquid. When added to the coating solution constituting the adjacent layer or another layer, the silver potential of the surface layer can be adjusted by diffusion during coating and drying. Further, an aqueous solution for adjusting the silver potential may be added to the coating solution for forming all the layers on the photosensitive layer side.

(Hardener) In the invention according to claim 8, the non-photosensitive layer furthest from the support contains the fluorine-based surfactant, and at least one of the constituent layers has the general formula ( It is characterized in that the film is hardened with at least one compound selected from 2) and the general formula (3), and it has been found that by adopting this structure, excellent effects of the present invention can be exhibited. .

In the general formula (2) or (3),
Examples of the m-valent group having a hydroxyl group represented by A and the n-valent group having an amide group represented by B include a non-cyclic hydrocarbon group having 1 to 10 carbon atoms having a hydroxyl group or an amide group (preferably Is an alkylene group having 1 to 8 carbon atoms), a 5- or 6-membered heterocyclic ring having a nitrogen, oxygen or sulfur atom, a 5- or 6-membered alicyclic group, or an aralkylene group having 7 to 10 carbon atoms. These groups may be substituted with a carboxy group (such as a methoxy group or an ethoxy group), an alkyl group having 1 to 4 carbon atoms, a halogen atom, an acetoxy group, or the like, and may be substituted via the hetero atom, carbonyl group, or carbamide group. They may be connected to each other.

Hereinafter, specific examples of the hardener represented by the general formula (2) will be given, but the present invention is not limited to these.

VS-1: CH ₂ ＣＨCHSO ₂ CH ₂ CH
_{(OH) CH 2 SO 2 CH} = CH 2 VS-2: CH 2 = CHSO 2 CH 2 C (OH) HC (O
_{H) HCH 2 SO 2 CH =} CH 2 VS-3: CH 2 = CHSO 2 CH 2 C (OH) HCH 2 C
_{(OH) HCH 2 SO 2 CH} = CH 2 VS-4: (CH 2 = CHSO 2 CH 2 C (OH) HC
H ₂ ) ₂ CO VS-5: (CH ₂ ＣＨCHSO ₂ CH ₂ C (OH) HC
_{H 2) 3 CCH 3 VS-} 6: (CH 2 = CHSO 2 CH 2 C (OH) HC
_{H 2) 2 O VS-7} : (CH 2 = CHSO 2 CH 2 C (OH) HC
H ₂ ) ₂ NH

[0091]

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Hereinafter, specific examples of the hardener represented by the general formula (3) will be given, but the present invention is not limited thereto.

[0093]

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[0094]

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Each of these hardeners is disclosed in US Pat.
73, 481 and the like. The amount of each hardener added was 1 g of hydrophilic colloid.
It is used in an amount of about 1 to 25 mg, preferably 2 to 20 mg.

The hardener represented by the general formulas (2) and (3) may be added to either the photosensitive layer or the non-photosensitive layer. It is more preferable because the influence on the photographic characteristics is small. More preferably, it is added to at least the protective layer which is a non-photosensitive layer forming the outermost surface layer of the photographic constituent layer.

(Coating method) In the ninth aspect of the present invention, the non-photosensitive layer farthest from the support contains the fluorine-based surfactant, and the number of constituent layers is 10 or more. By using this coating method, it is possible to improve various problems that occur in simultaneous multi-layer coating.

According to the ninth aspect of the present invention, the silver halide color photographic light-sensitive material may have at least 10 photographic constituent layers, and these may be formed by simultaneously applying multiple layers. Even if the photographic constituent layer composed of 10 or more layers is formed on the running support by one simultaneous multi-layer coating, or the coating is performed in two or more steps, and at least one coating is performed with 10 or more layers. The photographic constituent layer may be formed by a certain simultaneous multilayer coating method.

The simultaneous multi-layer coating of 10 or more photographic constituent layers can be performed by using a known coater head having a number of coating blocks corresponding to the number of layers.

In the invention according to the ninth aspect, from the viewpoint of improving the productivity, all the photographic constituent layers (including the silver halide emulsion layer required by one multi-layer simultaneous multi-layer coating) (however,
(A subbing layer which is a layer adjacent to the support and the photographic constituent layer is excluded). When all the photographic constituent layers including the necessary silver halide emulsion layer are coated by one multi-layer simultaneous multi-layer coating, or the coating is performed in two or more times, and at least one coating is performed in 10 or more layers. When the photographic constituent layer is applied by the simultaneous multi-layer coating method, the viscosity of the coating liquid for forming the lowermost layer adjacent to the support is preferably 15 to 100 cp. If it is less than 15 cp, coating unevenness tends to occur,
If it exceeds 100 cp, the uniformity of the coating film becomes poor, and the coating liquid tends to run out at both ends of the coating coater. A more preferred viscosity is 20 to 70 cp, and particularly preferred is 20 to 60 cp.

When the product is completed by one multi-layer simultaneous multi-layer coating, or when the coating is divided into two or more times and the simultaneous multi-layer coating method in which at least one coating is 10 layers or more is performed, The coating liquid viscosities of the ninth and higher constituent layers successively applied on the lower layer (first layer) are all 20 cp or more, and the arithmetic of the viscosities of the ninth and higher coating liquids. It is preferable to adjust the average to be 20 to 300 cp.

In particular, the viscosity of the non-photosensitive layer farthest from the support containing the fluorine-containing surfactant according to the present invention is 3
It is preferably 0 to 80 cp, particularly 40 to 60 c
It is preferably p.

The viscosity of each coating solution can be adjusted to a predetermined value by adding a known thickener aqueous solution. As the thickener, poly (sodium p-styrenesulfonate) or the like can be used. In addition, a sulfonic acid group or a sulfonic acid group described in JP-A-63-11934 can be used.
Vinyl polymers having sulfate esters, carboxyl groups or salts thereof can also be used.

The viscosity was measured using, for example, a B-type viscometer (manufactured by Tokyo Keiki Co., Ltd .: Model BL) with a shear rate of 29.8.
mm / sec (rotor No. 1, 30 rpm, temperature 40
° C).

The coating amount of each layer in the photographic material of the ninth aspect is preferably 3 ml / m ² or more. If the coating amount is less than the above range, coating unevenness occurs, making it impossible to perform uniform multilayer simultaneous coating on the support. More preferably, the coating liquid amount of each layer is 4 to 30 ml / m ² .
If the coating liquid amount of any one of the constituent layers is 30 ml / m ² or more, and if 10 or more layers are simultaneously coated, the applied layers tend to easily shift between the applied constituent layers, which is not preferable.

When the product is completed by one multi-layer simultaneous multi-layer coating, or the coating is performed in two or more times,
When the coating is performed by the simultaneous multi-layer coating method in which at least one coating is at least 10 layers, the total amount of the coating liquid of the lowermost layer adjacent to the support and the total of 9 or more layers applied adjacent to the lowermost layer Is preferably 250 ml / m ² or less. When two lowermost layers, for example, an antihalation layer and an intermediate layer, are applied separately from the multi-layer simultaneous multi-layer coating, the total amount of simultaneous coating liquids of all the 10 or more layers is 250 m.
It is preferably 1 / m ² or less. If the upper limit is exceeded, the applied layer is likely to be misaligned between the constituent layers to be applied. Further, in consideration of the drying load in the drying step, the more preferable total amount of the coating liquid is 200 ml / m ² or less.

The simultaneous multi-layer coating is described in JP-B-33-897.
No. 7, etc., using a multilayer simultaneous coating apparatus. For example, as shown in FIG. 1 described in JP-B-33-8977 and the like, a slide hopper type coating apparatus capable of simultaneously coating 10 or more layers with the same type as the slide hopper type of n-layer simultaneous coating is used. It is possible to apply a predetermined coating liquid to ten or more slits and to apply the liquid so that the liquids overlap each other when flowing down the slide surface.

According to this slide hopper type coating apparatus, 10 to 20 layers can be simultaneously coated, but in the present invention, 11 to 18 layers of simultaneous multilayer coating are preferable.

Generally, the coating speed is 30 to 500 m / m
in, preferably 60 to 300 m / min,
More preferably, it is 80 to 250 m / min.

The applied constituent layers are dried by a usual method. That is, the applied constituent layers are cooled and solidified immediately after the application, and then dried.

The coagulation is usually carried out at a dry bulb temperature of -10 to 20 ° C.
This is done in contact with low-temperature air. After the coating film is cooled and solidified, drying is performed by blowing a conventionally used gas. Drying by this wind usually has a dry bulb temperature of 1
5 to 45 ° C, 10 to 50% RH relative air
This is done by blowing at a flow rate of 40 m ² / min. This method is preferable because it can prevent an increase in fog due to drying. The required drying time varies depending on the water content of the photosensitive material to be coated, the amount of the coating solution, and the drying conditions, but the drying time is usually 0.5 to 5 minutes. The coating film thus dried is preferably wetted with air having a dry bulb temperature of 20 to 40 ° C. and a relative humidity of 50 to 70% RH.

(Anionic Surfactant, Cationic Surfactant) In the invention according to claim 10, the non-photosensitive layer farthest from the support contains a mixture of an anionic surfactant and a cationic surfactant. In addition, at least one of them is a compound represented by the general formula (1), and by adopting this configuration, the antistatic effect can be significantly improved while maintaining the above effects.

The anionic surfactant represented by the general formula (1) and the cationic surfactant represented by the general formula (1) have a partial chemical structure of Rf- (O-Rf ') _n It is preferable that the-part is approximate, and it is particularly preferable that they are the same.

The expression “approximately” means that the difference in the number of carbon atoms in the above-mentioned partial chemical structure between the anionic surfactant and the cationic surfactant is within 3 or the difference in the number of fluorine atoms is within 6. Means that.

Further, it is more preferable that the partial chemical structures including L which is a mere bond or a linking group are similar.

(Constituent factors of silver halide color photographic light-sensitive material) The respective constituent factors of the silver halide color photographic light-sensitive material of the present invention except for the above-mentioned items will be described below.

The silver halide emulsion used in the silver halide color photographic light-sensitive material of the present invention is described in JP-A-61-1986.
No. 6643, No. 61-14630, No. 61-1121
No. 42, No. 62-157024, No. 62-18556
No. 63-92942, No. 63-151618,
No. 63-163451, No. 63-220238, No. 63-31244, Research Discl
Osure (hereinafter simply abbreviated as RD) 38957, I and III, RD40145 XV and the like can be used.

When the light-sensitive material of the present invention is constituted by using a silver halide emulsion, the silver halide emulsion is subjected to physical ripening,
It is preferable to use those that have been subjected to chemical ripening and spectral sensitization. The additive used in such a process is RD3
Nos. IV and V of 8957 and XV of RD40145.

Known photographic additives that can be used in the present invention include RD38957, Item II-X and RD4014.
Those described in the section I-XIII of No. 5 can be used.

In each of the red, green and blue light-sensitive silver halide emulsion layers of the silver halide color photographic light-sensitive material of the present invention, a coupler can be contained. It is preferable that the coloring dye formed from the coupler contained in each of these layers has a spectral absorption maximum separated by at least 20 nm. As the coupler, it is preferable to use a cyan coupler, a magenta coupler, and a yellow coupler. As a combination of each emulsion layer and a coupler, a combination of a yellow coupler and a blue photosensitive layer, a combination of a magenta coupler and a green photosensitive layer, a combination of a cyan coupler and a red photosensitive layer are used, but are not limited to these combinations. , And other combinations.

In the present invention, a DIR compound can be used. Specific examples of DIR compounds that can be used include, for example, D-1 to D-34 described in JP-A-4-114153, and these compounds can be preferably used in the present invention.

DIR that can be used in the present invention
Specific examples of the compounds other than those described above include, for example, U.S. Pat. Nos. 4,234,678, 3,227,554, 3,647,291, 3,958,993,
No. 4,419,886, No. 3,933,500
No., JP-A-57-56837, and JP-A-51-13239.
No. 2,072,363, US Pat.
No. 0,266, RD40145, XIV, and the like.

Further, specific examples of the coupler that can be used in the present invention are described in RD40145, section II and the like.

The additive used in the present invention is RD4014
It can be added by the dispersion method described in section VIII of 5, etc.

In the present invention, the aforementioned RD38957
Known supports described in Section XV and the like can be used.

The light-sensitive material of the present invention includes the aforementioned RD3895
Auxiliary layers such as a filter layer and an intermediate layer described in the section 7 XI can be provided.

The light-sensitive material can have various layer structures such as a normal layer, a reverse layer, and a unit structure described in RD38957, section XI.

The silver halide emulsion according to the present invention can be used for various color light-sensitive materials represented by color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers. Can be preferably applied.

To develop the silver halide color light-sensitive material of the present invention, for example, T.I. H. James, Theory of the Photographic Process 4th Edition (The Theory of The Photog
rafic ProcessForth Edition
n) Pages 291-334 and Journal of the
American Chemical Society (Journa1
of the American Chemical
Society, 73, 3,100 (195
The developer known per se described in 1) can be used, and XVII-XX of RD38957 described above can be used.
And development processing can be carried out by a usual method described in Section XXIII of RD40145.

[0130]

EXAMPLES The present invention will be described below in detail with reference to examples, but embodiments of the present invention are not limited thereto.

Example 1 (Preparation of photosensitive material sample 101) Thickness 12 provided with undercoat layer
Each of the constituent layers shown in Tables 2 to 4 was coated on a 5 μm cellulose triacetate film support to prepare a photosensitive material sample 101.

[0132] In all the following examples, the addition amount of each additive in a silver halide color photographic light-sensitive material showed especially in grams per 1 m ² unless otherwise noted. Also,
Silver halide and colloidal silver were shown in terms of metallic silver, and sensitizing dyes were shown in moles per mole of silver halide.

[0133]

[Table 2]

[0134]

[Table 3]

[0135]

[Table 4]

Incidentally, in addition to the above composition, compound SU-
1, SU-2, viscosity modifier V-1, hardener H-1, H-
2. Stabilizers ST-1, ST-2, antifoggant AF-
1, AF-2, AF-3, dyes AI-1, AI-2, A
I-3 and preservative D-1 were appropriately added to each layer. However, the gelatin used for the 14th layer had a Ca ion content of 1
It has an isoelectric point of 4.8 ppm. The hardeners H-1 and H-2 were added to the coating liquids of the thirteenth and fourteenth layers by in-line mixing just before coating, and the coating amounts of each were 0.15 g / m ² , 0.1. 09 g / m ² .

Table 5 shows details of the emulsions used in the above samples. In addition, the average particle diameter in the table was shown by the particle diameter converted into a cube.

[0138]

[Table 5]

The silver iodobromide emulsions b, e, g and h contained iridium in an amount of 1 × 10 ^-7 to 1 × 10 ^-6 mol / 1 mol Ag.
Contains.

Emulsions other than the above silver iodobromide emulsion i were added with each of the sensitizing dyes shown in the table and then added with sodium thiosulfate, chloroauric acid, potassium thiocyanate, etc. Chemical sensitization was performed to optimize the relationship.

The total silver coating amount (silver coating amount in terms of metallic silver) of photosensitive material sample 101 was 3.26 g / m ² .

The compounds used in the preparation of the photosensitive material 101 are described below.

[0143]

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[0144]

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[0145]

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[0146]

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[0147]

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[0148]

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[0149]

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[0150]

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[0151]

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(Preparation of Photosensitive Material Samples 102 to 110) In Sample 101 prepared above, S
In place of U-3, each of the surfactants shown in Table 6 was added so as to obtain substantially the same dynamic surface tension, and in place of the matting agent PMMA, the present invention also shown in Table 6 was used. Sample 1 was prepared in the same manner except that the monodispersion was changed to high monodispersion P-1
Nos. 02 to 110 were produced.

[0153]

[Table 6]

[0154]

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The average particle size of each matting agent in Table 6 was 3.0 μm and the coating amount was 0.15 g / m 2.
^{And 2} .

(Evaluation of Characteristics of Each Sample) The following evaluation was performed for each sample prepared as described above.

[Evaluation of Blocking Property]
mm, 1 m in length, and conditioned at 40 ° C. and 80% RH for 24 hours.
It was wound with a tension of N / cm and left under the same atmosphere for 3 days. Thereafter, the sample was unwound and the state of coating film destruction due to blocking of the surface (so-called front and back surface adhesion) was visually observed in accordance with the following criteria. In this evaluation, if the rank is B or more, it is determined that there is no practical problem.

A: No change in surface layer B: Destruction is observed in an area of less than 10% of the surface layer C: Destruction is observed in an area of 10% to less than 40% of the surface layer D: 40% of the surface layer Destruction is seen in the above area.

[Evaluation of Charging Characteristics]
After humidifying for 24 hours in a dark room under an atmosphere of 5% RH, the unexposed samples are placed one on top of the other, spread and pressed by a rubber roller from above, and then each sample is peeled off.
Static electricity is generated, color development is performed in accordance with the method described in paragraphs [0220] to [0227] of JP-A-10-123652, and the degree of generation of static marks is determined according to the following evaluation criteria. It was visually evaluated. In this evaluation, if the rank is B or more, it is determined that there is no practical problem.

A: No static mark is observed. B: Some static mark is generated. C: Static mark is considerably generated. D: Static mark is significantly generated. E: Static mark is generated. Tick marks are generated on the entire surface. [Evaluation of Tape Adhesion] Under an atmosphere of 20 ° C. and 65% RH, a 25 mm wide adhesive tape (3M
No. 8422), and after 1 minute, the tape was pulled in the opposite direction in a color developing solution for color negative film (CNK-4 color developing solution manufactured by Konica Corporation) to perform peeling, and the peeling resistance at that time was measured. The adhesiveness to the adhesive tape was evaluated from the peel resistance. Peel resistance is 300g /
If it is greater than inch, no tape peeling trouble occurs. The term “inch” in the present invention indicates 2.54 cm.

A: Peel resistance of 330 g / inch or more B: Peel resistance of 300 g / inch or more and 330 g / in
Less than ch C: Peeling resistance is 270 g / inch or more and 300 g / in
Less than ch D: The peel resistance is less than 270 g / inch.

[0162]

[Table 7]

As is clear from Table 7, one of the photographic constituent layers
The photosensitive material sample of the present invention containing the fluorine-containing surfactant according to the present invention in the layer, and containing the monodisperse matting agent, has improved blocking properties, improved charging properties, and improved tape adhesion. I was able to confirm that.

Example 2 In the above-prepared sample 101 of Example 1, each surfactant described in Table 8 was replaced with SU-3 of the fourteenth layer so that substantially the same dynamic surface tension was obtained. Sample 201 was added in the same manner except that the matting agent (PMMA) of the 14th layer was added and the matting agent described in Table 8 was used.
To 207 were produced.

[0165]

[Table 8]

In the table, the average particle size of each matting agent was 3.0 μm, and the coating amount was 0.15 g / m ^2.
And

The following evaluation was performed on each of the samples manufactured as described above and the sample 101 manufactured in Example 1.

[Evaluation of Blocking Property] The evaluation was performed in the same manner as in Example 1.

[Evaluation of Sliding Property] Each sample was heated at 23 ° C. and 60 ° C.
After conditioning for 24 hours in an atmosphere of% RH, the sample was fixed on a sample base with the back surface of the sample (the surface opposite to the surface coated with the photosensitive layer) facing upward. Then, the sample was attached to a stainless steel fitting having an attachment surface area of 1 cm ² with the second protective layer facing outward, and the sample was placed such that the second protective layer of the sample of the fitting and the sample back surface of the sample table were in contact with each other. The sample table was moved at a speed of 1 cm / sec, a dynamic friction coefficient (μK) was determined by a known method.

[Evaluation of Film Feeding Torque] Each sample was conditioned at 23 ° C. and 60% RH for 24 hours, then sealed in a state of being wound in a cartridge according to APS size standard, and left at 55 ° C. for 24 hours. I left it. Then, the shaft torque (g · cm) during the rotation drive was measured. If the measured value is 250 g · cm or more, it is judged that there is a risk of troubles in the camera and the like, which is not preferable.

[Evaluation of Tape Adhesiveness] The evaluation was performed in the same manner as in Example 1.

Table 9 shows the results of the respective samples obtained as described above.

[0173]

[Table 9]

As is clear from Table 9, the light-sensitive material sample of the present invention in which the non-photosensitive layer furthest from the support contains the fluorinated surfactant and the alkali-soluble matting agent of the present invention has a tape adhesive property. It can be seen that the blocking property and the sliding property were improved without any problem, and the feeding torque was reduced.

Example 3 In the above-prepared sample 101 of Example 1, each surfactant described in Table 10 was replaced with SU-3 in the fourteenth layer so that substantially the same dynamic surface tension was obtained. Addition, also
Samples 301 to 3 were prepared in the same manner except that the aqueous polyurethane dispersion was added to the fourteenth layer as shown in Table 10.
10 was produced.

[0176]

[Table 10]

In the table, [1] indicates the above-mentioned Witco Wi
tcobond W242, [2] is Zeneca R
Neorez R966, manufactured by Esins Co., Ltd., and the amount of each addition is indicated by the coating amount per unit area as the solid content.

The following evaluation was performed on each sample manufactured as described above and the sample 101 manufactured in Example 1.

[Evaluation of Blocking Property] The evaluation was performed in the same manner as in Example 1.

[Evaluation of Sliding Property] The evaluation was performed in the same manner as in Example 2.

[Evaluation of Scratch Resistance] Each sample was heated at 23 ° C. and 55%
After conditioning for 24 hours in an atmosphere of RH, a sapphire needle having a spherical portion at the tip having a diameter of 30 μm was vertically applied to the surface, and the surface was scratched at a speed of 10 mm / sec by applying a continuously changing load of 0 to 50 g. Each sample after scratching was observed with transmitted light, and the load value (g) at which scratches became visible was used as a measure of scratch resistance. In addition,
The numerical value was obtained as an arithmetic mean value of five measurements, and it was determined that the larger the numerical value, the better the scratch resistance.

[Evaluation of Tape Adhesion] The evaluation was performed in the same manner as in Example 1.

Table 11 shows the results of each sample obtained as described above.
Shown in

[0184]

[Table 11]

As is clear from Table 11, the light-sensitive material sample of the present invention in which the non-photosensitive layer furthest from the support contains the fluorine-containing surfactant and the aqueous polyurethane according to the present invention has a blocking property and a sliding property. It was confirmed that the sheet had excellent scratch resistance and tape adhesion.

Example 4 In the above-prepared sample 101 of Example 1, each surfactant described in Table 12 was replaced with SU-3 of the fourteenth layer so that substantially the same dynamic surface tension was obtained. Addition, also
In the 14th layer, the slip agents described in Table 12 were also used.
In the same manner except that the sample 401 was changed as described in
To 408.

[0187]

[Table 12]

For each of the samples manufactured as described above and the sample 101 manufactured in Example 1, the method described above was used.
The evaluation of the blocking property, the evaluation of the charging property, the evaluation of the scratch resistance and the evaluation of the tape adhesiveness were performed. The obtained results are shown in Table 13.

[0189]

[Table 13]

As is clear from Table 13, the light-sensitive material sample of the present invention in which the non-photosensitive layer furthest from the support contains the fluorine-based surfactant and the polyorganosiloxane according to the present invention has a tape adhesive property. It was confirmed that there was no problem and the blocking property, the charging property, and the scratch resistance were excellent.

Example 5 In the above-prepared sample 101 of Example 1, each of the surfactants described in Table 14 was replaced with SU-14 in the fourteenth layer so that substantially the same dynamic surface tension was obtained. Addition, also
14th layer binder (normal lime-processed gelatin: Ca
Ion 1500 ppm, isoelectric point 4.8)
Samples 501 to 508 were produced in the same manner except that the binder described in No. 4 was used.

[0192]

[Table 14]

For each of the samples manufactured as described above and the sample 101 manufactured in Example 1, the method described above was used.
The evaluation of the charging characteristics, the evaluation of the scratch resistance, the adhesiveness of the tape, and the evaluation of fogging were carried out by the methods described below. The obtained results are shown in Table 15.

[Evaluation of fog] Each sample was subjected to 40 ° C., 65%
After being left for 3 days in an RH atmosphere and subjected to a forced deterioration treatment, the sample was treated with a light source at 5400 ° K together with the untreated sample for 1 hour.
Exposure was performed at / 200 seconds through a step wedge, and the above-described color development processing was performed. Each developed sample is represented by X
The transmission density of the unexposed part was measured with blue light using a densitometer manufactured by -rite, and the increase in fog (ΔF *) due to forced deterioration was determined.

* ΔF = density of unexposed part of sample subjected to forced deterioration−density of unexposed part of untreated sample

[0196]

[Table 15]

As is clear from Table 15, the light-sensitive material of the present invention wherein the non-photosensitive layer furthest from the support contains the fluorine-containing surfactant according to the present invention and the binder contains ion-exchanged gelatin. It was confirmed that the sample had no problem with the tape adhesiveness, the scratch resistance and the improvement of the charging characteristics were confirmed, and further, the fog hardly occurred.

Example 6 In the above-prepared sample 101 of Example 1, each surfactant described in Table 16 was replaced with SU-3 of the fourteenth layer so that substantially the same dynamic surface tension was obtained. Addition, also
Samples 601 to 610 were prepared in the same manner except that the film surface pH and the coating silver potential of the fourteenth layer were similarly changed to the values shown in Table 16.
Was prepared.

[0199]

[Table 16]

The samples prepared as described above and the sample 101 prepared in Example 1 were subjected to the above-described method.
The evaluation of the blocking properties, the evaluation of the charging properties, the evaluation of fog, the adhesiveness of the tape, and the aggregation state of the coating liquid were performed by the methods described below. The results are shown in Table 17.

[Evaluation of Aggregation Condition] The coating solution for the 14th layer prepared in the preparation of each sample was slowly stirred at 40 ° C.
After 4 hours, the presence or absence of agglomerates in the coating solution was observed with a 200-power optical microscope, and evaluated on a 5-point scale according to the evaluation criteria described below. In addition, if the rank was A or B, it was determined to be within a range in which there was no problem in manufacturing.

A: No generation of aggregates is observed. B: Generation of small aggregates is slightly observed.

C: Small aggregates are observed. D: Generation of large aggregates is slightly observed.

E: Generation of large and small aggregates is remarkable.

[0205]

[Table 17]

As is clear from Table 17, the non-photosensitive layer furthest from the support contains the fluorine-containing surfactant according to the present invention, and the pH of the film surface of the light-sensitive material is 5.6 to 6.2. The photosensitive material sample of the present invention in which the silver potential of the coating film is in the range of 80 to 150 mV has no problem in tape adhesion, has excellent blocking properties and charging properties, and is less likely to cause fog. Further, it was confirmed that the generation of aggregates was small even when the coating solution was stored for a long period of time.

Example 7 In the above-prepared sample 101 of Example 1, instead of SU-3 of the fourteenth layer, each of the surfactants described in Table 18 was used so that substantially the same dynamic surface tension was obtained. Addition, also
Samples 701 to 706 were produced in the same manner except that the hardener H-1 alone was replaced with the hardener shown in Table 18 by the same mass.

[0208]

[Table 18]

With respect to each of the samples manufactured as described above and the sample 101 manufactured in Example 1, the following method was used.
Evaluation of blocking properties, evaluation of fog, evaluation of tape adhesion and scratch resistance were performed, and the obtained results are shown in Table 19.

[0210]

[Table 19]

As is clear from Table 19, the non-photosensitive layer furthest from the support contains the fluorine-containing surfactant according to the present invention and has at least one selected from the general formulas (2) and (3). It was confirmed that the light-sensitive material sample of the present invention hardened with one compound had no problem in tape adhesiveness, was excellent in blocking property and scratch resistance, and was hardly fogged.

Example 8 In the production of samples 101 and 104 described in Example 1,
Using a slide hopper type simultaneous multi-layer coating apparatus shown in FIG. 1 of JP-A-5-307229, the first to fourteenth layers were subjected to simultaneous multi-layer coating on the support at one time.

However, the coating speed was 150 m / min, the coating width was 1.27 m, the total coating length was 2,000 m, and the coating liquid temperature was 38 m / min.
° C, and the viscosity (cp) of each constituent layer was as follows.

First layer: 20, second layer: 85, third layer: 7
0, fourth layer: 50, fifth layer: 90, sixth layer: 70, seventh
Layer: 50, 8th layer: 80, 9th layer: 70, 10th layer: 5
5, 11th layer: 80, 12th layer: 70, 13th layer: 5
5, 14th layer: 60.

After coating under the above conditions, the sample obtained by drying was observed for surface defects (coating failure).
Sample 101, trailing fault defects average 5.5 pieces / 10 m ²
In contrast, the number of samples 104 was 2.0 / 10 m ²
The photosensitive material containing the fluorine-based surfactant according to the present invention in the non-photosensitive layer furthest from the support can be confirmed to be able to reduce coating failure even when 14 layers are produced by simultaneous multilayer coating. Was.

Example 9 In the above-prepared sample 101 of Example 1, instead of SU-3 of the fourteenth layer, each of the surfactants listed in Table 20 was prepared so that substantially the same dynamic surface tension was obtained. Samples 901 to 906 were prepared in the same manner, except that they were added in combination.

[0219]

[Table 20]

[0218]

Embedded image

With respect to each of the samples manufactured as described above and the sample 101 manufactured in Example 1, the method described above was used.
Evaluation of blocking properties, evaluation of fog, tape adhesion,
The evaluation of scratch resistance and the charging property 2 were performed by the methods described below, and the obtained results are shown in Table 21.

[Evaluation of Charging Characteristics 2] The charging conditions were evaluated under the same conditions as in Example 1 except that the test atmosphere of each sample was changed to 23 ° C. and 20% RH. The method
The evaluation was performed under lower humidity, and the conditions were severe.

[0221]

[Table 21]

As is clear from Table 21, the non-photosensitive layer furthest from the support contains a mixture of an anionic surfactant and a cationic surfactant, at least one of which is a fluorine-based surfactant according to the present invention. Photosensitive material sample,
It can be seen that there is no problem in the tape adhesiveness, the blocking property, the charging property 2 and the scratch resistance are excellent, and the increase in fog (ΔF) is reduced.

[0223]

According to the present invention, the blocking property, the charging property, the scratch resistance, the sliding property and the tape adhesiveness are excellent, the cohesion of the coating solution used for the production is improved, and the coating failure is reduced.
Further, a silver halide color photographic light-sensitive material having a small feeding-out torque of the light-sensitive material could be provided.

Claims (10)

[Claims] 1. A silver halide color photographic light-sensitive material having a red-sensitive layer, a green-sensitive layer, a blue-sensitive layer and a non-light-sensitive layer on one side of the support. A photosensitive layer comprising a compound represented by the following general formula (1):
A silver halide color photographic material comprising a monodisperse matting agent. Formula (1) H · Rf- (CH 2) in _n -L-X _m [wherein, Rf represents an alkylene group containing at least one fluorine atom, L represents a mere bond or a linking group, X Represents a hydroxy group, an anionic group, a cationic group or an amphoteric group. n represents an integer of 2 or more and 5 or less, and m represents an integer of 1 or more. ] 2. A silver halide color photographic light-sensitive material having a red-sensitive layer, a green-sensitive layer, a blue-sensitive layer and a non-light-sensitive layer on one side of a support, A photosensitive layer comprising a compound represented by the general formula (1);
A silver halide color photographic material comprising an alkali-soluble matting agent. 3. A silver halide color photographic light-sensitive material having a red-sensitive layer, a green-sensitive layer, a blue-sensitive layer and a non-light-sensitive layer on one side of a support, A photosensitive layer comprising a compound represented by the general formula (1);
A silver halide color photographic light-sensitive material characterized by containing an aqueous polyurethane. 4. A silver halide color photographic material having a red light-sensitive layer, a green light-sensitive layer, a blue light-sensitive layer and a non-light-sensitive layer on one side of a support. A photosensitive layer comprising a compound represented by the general formula (1);
A silver halide color photographic light-sensitive material comprising a polyorganosiloxane. 5. A silver halide color photographic light-sensitive material having a red-sensitive layer, a green-sensitive layer, a blue-sensitive layer and a non-light-sensitive layer on one side of the support, A photosensitive layer comprising a compound represented by the general formula (1);
A silver halide color photographic light-sensitive material characterized by containing ion-exchanged gelatin. 6. A silver halide color photographic light-sensitive material having a red-sensitive layer, a green-sensitive layer, a blue-sensitive layer and a non-light-sensitive layer on one side of the support, A photosensitive layer comprising a compound represented by the general formula (1);
A silver halide color photographic light-sensitive material comprising 10% by mass or more of non-photosensitive gelatin having an isoelectric point of 5.0 or more. 7. A silver halide color photographic light-sensitive material having a red-sensitive layer, a green-sensitive layer, a blue-sensitive layer and a non-light-sensitive layer on one side of the support, When the photosensitive layer contains the compound represented by the general formula (1) and the pH of the surface of the silver halide color photographic material is in the range of 5.6 to 6.2, the silver potential of the coating film is adjusted. Is 80
A silver halide color photographic light-sensitive material, which is within the range of from 150 mV to 150 mV 8. A silver halide color photographic light-sensitive material having a red-sensitive layer, a green-sensitive layer, a blue-sensitive layer and a non-light-sensitive layer on one side of the support, The photosensitive layer contains the compound represented by the general formula (1), and at least one of the constituent layers is hardened with at least one compound selected from the following general formulas (2) and (3). A silver halide color photographic light-sensitive material characterized in that: Formula _{(2) (CH 2 = CHSO} 2) m A general formula _{(3) (CH 2 = CHSO} 2) n B wherein, A represents an m-valent group having at least one hydroxyl group, B is Represents an n-valent group having at least one amide group. m represents an integer of 2, 3 or 4, n is 2,
Represents an integer of 3 or 4. ] 9. A silver halide color photographic light-sensitive material having a red-sensitive layer, a green-sensitive layer, a blue-sensitive layer and a non-light-sensitive layer on one side of the support, A silver halide color photograph, wherein the photosensitive layer contains the compound represented by the general formula (1), has at least 10 constituent layers, and is formed by simultaneous multi-layer coating. Photosensitive material. 10. A red-sensitive layer on one side of a support,
In a silver halide color photographic light-sensitive material having a green light-sensitive layer, a blue light-sensitive layer and a light-insensitive layer, the light-insensitive layer furthest from the support contains a mixture of an anionic surfactant and a cationic surfactant. A silver halide color photographic light-sensitive material, wherein at least one of the compounds is a compound represented by the general formula (1).